Amide-linked bis-quaternary ammonium compounds



Patented Sept. 25,1951

AMIDE-LINKED ms-oU'A'rEaNARY AMMONIUM COMPOUNDS Peter L. de Bonnevilleand Charles L. Levesque, Philadelphia, Pa., assignors to Rohm & HaasCompany, Philadelphia, Pa., a corporation of Delaware No Drawing.Application September 27, 1950,

. Serial No. 187,149

6 Claims. (Cl. 260-558) in their various isomeric forms, the relativeposi- This invention deals with compounds of the V tion of the alkylgroup on the benzene ring, the

formula n 4 R R n wherein R is methyl or ethyl, R is an alkyl group formof this alkyl group, and the presence of of seven to nine carbon atoms,R is hydrogen or one or more methyl substituents being but minor methyl,A is an ethylene or propylene group, variants. The alkylbenzyl halidesand tertiary CnHZrI, and X is an anion. These compounds are amines,which may be derived from them, are valuable bactericides andfungicides. They are based on alkylbenzenes such as (l-methylhexyl)characterized by good solubility-and effectiveness benzene,(l-ethylpentyl) benzene, (1,3-dimethylagainst many different types oforganisms at con- 1 propylbutyl) benzene. (1 methylheptyl) bensiderabledilution and'under adverse conditions. zene, (2-ethylhexylJbenzene,(l-ethylhexyDben- For instance, they are bactericidally active in zene,(3,5,5-trimethylhexyl)benzene, 0-, m-, or hard water and in the presenceof organic matep-octyltoluene, p-(l-methylheptyl) toluene, heprial.tylxylenes, pl-ethylpentyl) toluene, 1-ethyl-3- Many quaternary ammoniumcompounds sufier methylbutyhbenzene, and the like and mixtures aconsiderable decrease in activity in hard water of such compounds. Thealkyl group may be of and/ or in water contaminated with organicmastraight or branched chain structure and maybe terials which arenormally encountered in the primary, secondary, or tertiary. use ofthese compounds as disinfectants. These Known methods for introducingalkyl groups undesirable efiects do not appear or are miniin the benzenering may be used for preparation mized with the compounds of thisinvention. of the starting hydrocarbons. For example. an

The bis-quaternary ammonium compounds of acyl halide may be reached withbenzene or toluthis invention have amide linkages in the chain ene or axylene and the acyl group thus introbetween the quaternary nitrogens.They rely for duced reduced. Alkyl groups are also obtained theirhydrophobic portion upon N-alkylbenzyl from oleflnes or alcohols byknown methods. groups which have seven to nine carbon atoms Thealkylbenzenes are converted to alkylbenzyl in the alkyl radical. Whilebis-quaternary amhalides by halomethylation. The alkylbenzene is moniumcompounds with smaller or larger alkylreacted, for example, withformaldehyde and hybenzyl groups can be prepared, such compounds drogenchloride or hydrogen bromide in the presdo not exhibit the high phenolcoefiicients which 5 ence of a catalyst mixture of zinc chloride and arefound for the claimed compounds. 7 a lower aliphatic monocarboxylicacid, such as Compounds of the formula given above are formic, acetic,chloroacetic, or propionic. Acid prepared through a series of reactionswhich inanhydrides may be used in place of these acids volve analkylenediamine, a haloacetyl halide, a or in admixture therewith.Formaldehyde may secondary amine, and an alkylbenzyl halide. be used asa gas or as a revertible polymer. The The reactions may be carried out,for example, equivalent of formaldehyde and hydrogen chlowith analkylenediamine, a haloacetyl halide, and ride or bromide is provided bya halomethyl ether. a tertiary amine having an N-alkylbenzyl sub- Themost effective ratio of zinc chloride to stituent which can be preparedfrom an alkylcarboxylic acid or anhydride is one mole of the benzylhalide and a secondary amine. Ethylformer to 1.5 to 8 moles of thelatter. For one enediamine and propylenediamlne are the dimoleequivalent of an alkylbenzene from one to amines of choice. Chloroacetylchloride is the 2.5 and pre e t0 M0168 0 o maldepreferred haloacetylhalide. Dimethylamines or diethylamines are the preferred secondaryamines zinc'chloride associated with the proportion of anddimethylalkylbenzylamines and diethylalkylcarboxylic acid stated.Reaction temperatures benzylamines are the preferred tertiary amines. of50 to 100 C. are eifective. By this method Either an alkylbenzylchloride or an alkylbenzyl good yields of alkylbenzyl halides areobtained bromide may be used. with introduction almost entirely of asingle The alkylbenzyl groups in the above compounds halomethyl groupand without formation of troumay be heptylbenzyl, octylbenzyl, ornonylbenzyl blesome resinous products.

hyde are used together with 0.5 to 2.5 moles of Examples of thepreparation or some typical alkylbenzyl halides lollow. weight.

Example 1 Commercial 3-heptano1 was dehydrated on an alumina catalyst at400 C. to yield a mixture of 2-heptene and B-heptene which was condensedand distilled.

There were mixed 125 parts or this product. 198 parts of benzene, and196 parts or concentrated sulfuric acid while the mixture was stirredand held at 5 C. The mixture was stirred for three hours with thetemperature of the mixture being allowed to advance above roomtemperature. Layers were permitted to form and the upper layer wastaken. It was twice washed with sulfuric acid and'distilled to yield 167parts of heptylbenzene, probably a mixture of 2-heptylbenzene and3-heptylbenzene. The product had a carbon content of 87.3% and ahydrogen content of 11.7%, compared with theoretical values '01 88.6%and 11.7 respectively.

There were mixed 160 parts of this product, 90 parts of anhydrous zincchloride, and 138 parts of glacial acetic acid. 'I'hereto was added at60 C. 106 parts of dichloromethyl ether. The mixture was stirred forfour hours and then allowed to stand and separate into layers. The upperlayer was washed with water, with sodium bicarbonate solution, and withwater and then distilled. At 127132 C./2 mm. there was obtained afraction of 128 parts which corresponded in composition to heptylbenzylchloride.

Example 2 A mixture of 95 parts by weight of octylbenzene .(chiefiy2-octylbenzene with some 3-octylbenzene), 30 parts of paraformaldehyde,54 parts of anhydrous zinc chloride, and 120 parts of glacial aceticacid was stirred at 50 C. while hydrogen chloride was passed in for twohours at a fairly rapid rate. The reaction mixture was Parts shown arebyallowed to stratify and the upper layer was taken,

washed with hot water, with a 10% sodium bicarbonate solution, and withhot water, dried over sodium sulfate and distilled. The forerun of partsconsisted of octylbenzene. There was then obtained at 119-121 C./mm. 71parts of octylbenzyl chloride.

Example 3 To a mixture of 46.5 parts of octylbenzene (chiefly2-octylbenzene), 17 parts of anhydrous zinc chloride, and 40 parts ofglacial acetic acid there was added dropwise 50 parts of bis-bromomethylether. The mixture was stirred and heated at 70 C. for four hours inall. Layers were allowed to form and were separated. The upper layer waswashed with hot water, with 10% sodium bicarbonate solution, and withwater. It was dried over sodium sulfate and distilled. At 155-174 C./2mm. there was obtained a fraction corresponding in composition tooctylbenzyl bromide. It contained by analysis 28.8% of bromine. Theoryfor this product is 28.3%.

Example 4 To a mixture of 70 parts of 2-ethylhexylbenzene (preparedaccording to the method of Sulzbacher and Bergmann, J. Org. Chem. 13,303 (1948)), 50.3 parts of anhydrous zinc chloride, and 60parts ofglacial acetic acid there was added with stirring 42.5 parts ofdichloromethyl ether over the course of an hour, while the reactionmixture was maintained at 60 C. Stirring was continued-for another twohours with the temperature held at 60 C.' Layerswere then Example 5 To amixture of 138 parts byweight of toluene and parts of anhydrous hydrogenfluoride, contained in a copper flask and held at 0-10 C.. there wasadded 336 parts of mixed octenes, boiling at 123-134 C., at such a ratethat the temperature did not rise above 10 C. The reaction mixture wasstirred for an hour and then poured upon ice. The organic layer wasseparated, washed with water, with 5% sodium'bicarbonate solution, andagain with water, dried over calcium chloride, and finally distilled.Unreacted toluene and octene were removed and the organic liquidstripped by heating to C./35 mm. There was then obtained a fractionbetween C./35 mm. and C./0.5 mm. which consisted essentially ofoctyltoluenes.

In the reaction vessel equipped with a stirrer a mixture was made of 32parts of octyltoluene, 25 parts of anhydrous zinc chloride, and 60 partsof glacial acetic acid. With the temperature kept at 50 to 60 C. therewas added thereto 20 parts of dichloromethyl ether. The temperature ofthe mixture was then raised to 90 C. for three hours. The reactionmixture was then separated into layers. The product layer-was washedwith water, with a 5% sodium bicarbonate solution, and again with water.Upon distillation a fraction was obtained at 133148 C./0.3 mm. whichcorresponded'in composition to 2- methyl-5-octylbenzyl chloride.

Example 6 To a mixture of 184 parts of toluene and 103 parts of sulfuricacid there was added 112 parts of octene while the mixture wasstirredand held at 5-13 C. The octene had been prepared by dehydrationof capryl alcohol on an alumina catalyst (of. Komarewski, Ulick, andMurray, J. Am. Chem. Soc. 67, 557 (1945)). The reaction mixture wasstirred for three hours at room temperature, and the product layer wasseparated. It was washed twice with concentrated sulfuric acid anddistilled. The fraction taken at 9395 C./0.3 mm. corresponded incomposition to sec.-octylmethylbenzene.

To a mixture of 81 parts of this product, 47.5 parts of anhydrous zincchloride, and 65 parts of glacial acetic acid there was added 46 partsof dichloromethyl ether while the mixture was stirred and held at 5060C. for an hour. It was stirred at 70-'l5 C. for four hours and allowedto form layers. The upper layer was separated, washed with water andsodium bicarbonate solution, and distilled. The fraction taken atl30-l50 C./0.3 mm. amounted to 43.8 parts and corresponded incomposition to methyloctylbenzyl chloride.

Example 7 Commercial diisobutyl carbinol was dipped slowly over a bed ofalumina at 400 C. The vapors were taken oil and condensed. Therefromnonene was separated and distilled at 7275 C./ 100 mm. The product,containing by analysis 85.7% of carbon and 14.3% of hydrogen, was2,6-dimethyl-3-heptene, for which the theoretical content of carbon is85.8% and of hydrogen is 14.3%.

There was added 135 parts by weight of this product to a stirred mixtureof 159 parts of henzene and 147 parts of sulfuric acid. The temperaturewas held between 0 and C. After the mixture had been stirred for threehours, it

was allowed to form. layers. The upper layer was distilled and thedistillate redistilled at 102106 C./3 mm. This distillate had amolecular weight of 203 (theory 204) and corresponded in composition tononylbenzene. The yield was 95 parts.

To a mixture of 80 parts of nonylbenzene, 40 parts of zinc chloride, and59 parts of glacial acetic acid there was added at room temperature 45parts of dichloromethyl ether. The mixture was stirred and heated at 70C. for three hours. It was then allowed to stand and form layers. Theupper layer was separated. washed with hot water, and with sodiumbicarbonate solution, dried over sodium sulfate, and distilled. Thefraction distilling at 141-142 C./2 mm. was nonylbenzyl chloride.

, Example 8 thereto was added dropwise with good agitation 126 parts ofpropylene trimer with the temperature at 25 30 C. Two hours were allowedfor the reaction. The reaction mixture was then permitted to formlayers, which were separated. The oil layer was washed and distilled atreduced pressure. The product, nonylbenzene, was collected at 127152C./27 mm.

A mixture was prepared from 612 parts of nonylbenzene prepared as above,205 parts of anhydrous zinc chloride, and 240 parts of glacial aceticacid and thereto was slowly added 345 parts of dichloromethyl ether withthe temperature at 55 C. The reaction mixture was then stirred for twohours with the temperature at 70 C. Layers were then separated. The oillayer was washed with hot water and with 10% sodium bicarbonate solutionand then stripped to yield crude nonylbenzyl chloride. distilled at128-152 C./1.5 mm. to give a product which corresponded very closely incomposi-' tion to theory.

Other alkylbenzyl or alkylmethylbenzyl halides can be prepared bysimilar methods. These halides are used in several ways. They may beconverted to tertiary amines by reaction with a secondary amine and theresulting tertiary amine reacted with an alkylene bis haloacetamide) togive a bis-quaternary ammonium salt.

Alternatively, the alkylbenzyl halide may be reacted with a his tertiaryamine formed by reaction of an alkylene bis(haloacetamide) and asecondary amine.

When the alkylbenzyl halides or alkylmethylbenzyl halides are convertedto tertiary amines to be reacted with an alkylene bis(haloacetamide),the conversion to tertiary amine is accomplished by reacting analkylbenzyl halide with a secondary amine such as dimethylamine ordiethylamine in the presence of an alkaline agent for taking up hydrogenhalide. An alkali metal This was hydroxide or an organic base, such aspyridine, or excess of the reacting amine may be used. Although thistype of reaction is conventional, specific examples will be given toillustrate a convenient procedure. The method is similar to thatdescribed for reacting benzyl chloride and dimethylamine (Ber. 42, 2593(1909) or Bull. soc. chim. (IV) 15, 168 (1915)) except that analkylbenzyl halide is used and the system need not be anhydrous. riedout in the presence of an inert organic solvent such as benzene,toluene, carbon tetrachloride, or the like. Thealkylbenzyldimethylamines or alkylbenzyldiethylamines may usually bepurified by distillation.

Procedures illustrating the step of forming alkylbenzyl dialkylaminesfollow.

Example 9 To a solution of eight parts of sodium hydroxide in 30 partsof water there was added 22.5 parts of an aqueous 40% dimethylaminesolution. The reaction vessel in which this mixture was prepared carrieda refluxing system cooled with Dry Ice and acetone. To the mixture therewas added 22.5 parts of heptylbenzyl chloride. The reaction mixture washeated to give gentle refluxing and dimethylamine was slowyl passed induring the course of three hours. Layers were then allowed to form'andwere separated. The product layer was washed with water until neutral tolitmus and was heated under reduced pressure. There was obtained 20parts of a light oil which gave the correct analysis forheptylbenzyldimethylamine.

This procedure was followed with 25.3 parts of nonylbenayl chloride inplace of the 22.5 parts of heptylbenzyl chloride shown above. There wasobtained nonylbenzyldimethylamine in a yield of 18 parts. The sameprocedure applied to an equivalent amount of octylbenzyl chlorideyielded octylbenzyldimethylamine. Substitution of equivalent weights ofdiethylamine led to the corresponding alkylbenzyldiethylamines.

In the series of reactions leading to bis-quaternary ammonium compoundsof this invention there are used ethylene or propylenebis(haloacetamides). These are prepared by reacting ethylenediamine orpropylenediamine with a haloacetyl halide, XCHzCOX where X is chlorineor bromine. This is conveniently accomplished in the presence of anorganic solvent and with the aid of a basic material for taking uphydrogen halide.

A convenient procedure for carrying out the above reaction isillustrated in the following example.

Example 10 There were mixed 75 parts of glacial acetic acid, 147 partsof anhydrous potassium acetate, and 75 parts of water. Thereto wasslowly added with stirring 30 parts of ethylenediamine and then withstirring and cooling 165 parts of chloroacetyl chloride. The reactionmixture was stirred for three hours. Then, 520 parts of a 25% aqueoussodium hydroxide solution was slowly added with cooling to render themixture slightly alkaline. The product separated as crystals which werefiltered off and recrystallized from methanol. The product melted at171173 C. and corresponded in composition to ethylene bis-(chloroacetamide). Cf. Jacobs and Heidelberger, J. Biol. Chem. 21, 151(1915).

The reaction is conveniently car- In the sameway there are reacted 3'1parts of propylenediamine .and 165 parts of chloroacetyl chloride togive propylene bis(chloroacetamide).

Reaction of an alkylene bis(haloacetamide) and andalkylbenzyldialkylarnine yields a hisquaternary compound. Approximatelyone mole of the former is reacted with two moles of the latter. The tworeactants may be mixed directly or in the presence of an organic solventsuch as benzene, toluene, xylene, isopropanol, butyl alcohol,isopropylether, a nitroparaflin such as nitromethane, acetonitrile,formamide, or the like. The'mixture is heated between 30 C. and about150 C., solvent may be driven off, and the quaternary ammoniumsaltrecovered as a'res-' idue. In some cases it is convenient toprecipitate this salt or to crystallize it.

Typicalpreparations by this method are described in the followingexamples.

Example 11 There were mixed 21.3 parts f propylene bis(chloroacetamide),52.5 parts of heptylbenzyldiethylamine, and 100 parts of toluene and themixture was heated under reflux for four hours. When the reactionmixture was cooled, a slurry resulted. This was extended with heptaneand filtered. A light-colored solid was thus obtained. This correspondsin composition to CzHs C2 s CzHs 'C2H5 c1H.5cH.oH zN-omo0NHoaHBNHcocuNonzoinicam 1 1 This compound has phenol coefficients of about 350 and450 against Salmonella typhosa and Staphylococcus aureus.

Example 12 CH3 CH3 CH3 CH:

Example 13 A mixture of 15.6 parts of ethylene bis(chloroacetamide),39.5 parts of nonylbenzyldimethylamine, and 40 parts of acetonitrile washeated under reflux for four and a half hours and left standingovernight. Crystals had then formed. They were filtered ofi and dried toyield 40.2 parts or product. This product corresponds in composition toon, on; on, on,

It has a phenol coefllcient of 350 against Salmonella typhosa and 500against Staphylococcus aureus.

Eatample 14 OH; CH; CE; /CH; CHaN-CHzC ONHCzHAC ONHCHr-NCHz It givesstable aqueous solutions at concentrations of 25% or more. It has phenolcoeflicients of 315 and 265 against Salmonella typhosa andStaphylococcus aureus respectively. It shows excellent activity in thebroth titer test against a variety of organisms, including S. pyogenes,N. catarrhalis, B. suis, C. welchii, and others.

An alkylene bis(haloacetamide) may be converted to a tertiary amine byreacting it with a secondary amine. For this purpose dimethylamine ordiethylamine are the secondary amines of first choice, although othersecondary amines can be used in this step. The reaction is best carriedout in an inert organic solvent and in the presence of an alkaline agentfor taking up hydrogen halide. An inorganic base such as caustic soda,an organic base such as pyridine, or excess of the secondary amine willserve this purpose. The reaction here is entirely comparable to thatdescribed above for converting an alkylbenzyl halide to a tertiary amine(cf. Von Braunand Miinch, Berichte 60, 349-351 (1927)).

Example 15 A mixture of 10.7 parts of ethylene bis-chloroacetamide and13.5 parts of dimethylamine gas dissolved in 40 parts of cold anhydrousethyl alcohol or benzene was heated under pressure for 24 hours at C.The bomb was chilled and carefully opened, the .dimethylaminehydrochloride removed by filtration, and the solvent stripped by warmingunder reduced pressure. The product resulting was ethylenebis(dimethylaminoacetamide) Example 16 By the procedure just describedthere were mixed 96parts of an aqueous 20% caustic soda solution and 3'7parts of diethylamine. Thereto was slowly added 114 parts of propylenebis- (chloroacetamide). The mixture was warmed for six hours with refluxfrom a chilled condenser. The reaction mixture was allowed to formlayers, which were separated. The organic layer was washed and driedover calcium sulfate. The product was propylenebis(diethylaminoacetamide).

The alkylene bis(aminoacetamides) are reacted with an aikylbenzyl halidein much the same 9 way as shown above for reacting an alkylenebis(haloacetamide) and an alkylbenzyldialkylamine. The reactants may becombined directly or, usually more conveniently, they are reactedtogether in an inert organic solvent such as benzene, toluene, isopropylether, isopropyl alcohol, butyl acetate, ethylene dichloride, formamide,or nitromethane. The reaction mixture is heated under reflux andthensolvent taken off or the product precipitated or crystallized.

Typical preparations of this kind follow.

Example 17 Example 18 There were mixed 30 parts of propylene bis-(diethylaminoacetamide), 48 parts of octylbenzyl chloride, and 70 partsof acetonitrile. This mixture was heated under reflux for six hours,allowed to stand overnight, and cooled. The product was precipitated. Itwas filtered ofl and dried. This product corresponds in composition toC2H5 CzHs CzHs orHt C8HnCuH4CHzN-CHzC ONHCaHuNHCOCHz-NCHzCaEhCaHn 1 1 Itis fairly soluble in water, stable in solution, stable in mixtures withbuilders such as sodium phosphate, pyrophosphate, and the like, stablein aqueous solutions of such mixtures and peculiarly effective as adisinfectant. It has a phenol coeflicient of 850 against Salmonellatyphosa.

Example 19 The above preparation was repeated with substitution of 57parts of octylbenzyl bromide for the above chloride. The product wassoluble and stable with a phenol coeflicient of 900 against Salmonellatyphosa.

Example 20 The above preparation was repeated with 51 parts ofoctylmethylbenzyl chloride. The product was a soluble, stable, effectivecompound having phenol coeflicients of 950 and 980 against Salmonellatyphosa and Staphylococcus aureus respectively.

Typical compounds of this invention were evaluated by determination ofthe greatest effective dilutions at which the compounds were eifec- 6otive bactericidally and bacteriostatically against a wide variety ofbacteria, both Gram-positive and Gram-negative. The evaluation was basedon a method of successive dilution in which a trypticase-soy broth wasutilized. One percent solutions of the products to be tested werediluted with the broth. The resulting dilutions were autoclaved for tenminutes at 10 to 12 pounds pressure. The dilutions were then cooled andinoculated with a four millimeter loopful of a R @cnlfomo oNHcmhNncocH;

10 culture of a test organism. tions were incubated at 37 C. for 24hours. The highest dilution showing no growth gave the value forbacteriostatic action. The dilutions were then incubated for a second 24hour period at 37 C. Subcultures were then made by transferring threeloopfuls from cultures showing no growth to fresh broth. The resultingsubcultures were incubated for 48 hours at 37 C. The highest dilutionshowing no growth was the endpoint for bactericidal action.

Typical of data obtained are those given in the table, wherein resultsare presented for ethylene The inoculateddilubis(oc'tylbenzyldimethylammonium chloride acetamide).

TABLE Efiective dilutions for the N-octylbenzyl compound EffectiveDilution Organism Gram-typo Bacteriostatic Bactericidal S. aureus 1:512.000 1:256,000 S. purogenes. 1:1.000. 000 1:1, 000.000 S. calls"12512.000 1:16.000 N. catarrhalw 1:512, 000 1:64, 000 S. luphosal:256,000 1:4,00.) P. aerugz'noaa 1232,000 1:1,000 P. vulgar-is. 4:4,0001:1,000 B. sui8. 1:512,000 1:8,000 1:64,000 l:04,000

Results with other compounds of this invention are similar. The resultsdemonstrate that these compounds are effective at relatively lowdilutions against organisms which are often diflicult to control.

An even more striking evaluation of compounds of this invention is basedon activity in hard water and in the presence of organic contaminants.For example, in water having a hardness equivalent to 400 parts permillion as calcium carbonate the compounds of this invention give killsof 99.9% within 30 seconds at concentration of compound of 50 parts permillion. Typical commercial quaternarieswere tested under the sameconditions. Compound A required over 60 seconds at 50 P. P. M. CompoundB required over 300 seconds at 50 P. P. M. Compound C failed to give a99% kill in 300 seconds even at 200 P. P. M.

Evaluations were made in water having a hardness of 30 grains per gallonto which one percent of an ice cream mix was added. A 99.9% kill wasobtained in less than 30 seconds with 200 P. P. M. of the N-octylbenzylquaternaries of this invention. The nonylbenzyl quaternaries gave a99.9% kill at 200 P. P. M. in less than one minute, while this kill wasobtained with ethylene bis(nonylmethylbenzy1 dimethyl ammonium chlorideacetamide) in less than two minutes. Available commercial quaternariesrequired over five minutes at 200 P. P. M.

The test method used in the above evaluations was based on the Oval TubeMethod of F. W. Barber, in which 'a synthetic hard water is used and theorganic contaminant is an ice cream mix.

We claim:

1. Compounds of the structure wherein R is an alkyl group of not overtwo car-. bon atoms, R is an allgvl group of seven to nine carbon atoms,R. is a. member of the class consisting of hydrogen and the methylgroup, X is an anion, and n is an integer from two to three. 5

2. A compound of the structure C1Hu CE; CH: CE; /CH: 01H" QOHr-N-omCONHQmNHcOCm-N-CBG $1 $1 3. A eompound of the structure cm" 05; emout cm on!" CHr-NC!hC0NBC HNHG0CHa-NCHO t, a 4. A compound 0! thestructm'e 0.11- cg. cm 05. cm 0.11"

CHa-NCHaCONHGaHNHCOCHr-N-CH 1 1 5. A compound of the structure CaHn CH4CH: CH: CH: Conn 6. A compound of the structure C'Hfl CH; CH: CH: CH:01H" PETER L. n: BENNEVILLE. CHARLE L. IEVESQUE- No references cited.

1. COMPOUNDS OF THE STRUCTURE